WO2014175212A1 - Dispositif de stockage d'énergie électrique - Google Patents

Dispositif de stockage d'énergie électrique Download PDF

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WO2014175212A1
WO2014175212A1 PCT/JP2014/061163 JP2014061163W WO2014175212A1 WO 2014175212 A1 WO2014175212 A1 WO 2014175212A1 JP 2014061163 W JP2014061163 W JP 2014061163W WO 2014175212 A1 WO2014175212 A1 WO 2014175212A1
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negative electrode
active material
positive electrode
ceramic layer
ceramic
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PCT/JP2014/061163
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English (en)
Japanese (ja)
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亨 永浦
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永浦 敦子
永浦 千恵子
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Publication of WO2014175212A1 publication Critical patent/WO2014175212A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H01M50/434—Ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a power storage device. Specifically, the present invention relates to a power storage device in which a ceramic layer having high heat resistance is used as a separator and internal short circuit is sufficiently prevented and internal resistance is sufficiently low.
  • Lithium ion batteries which have been widely used as power sources for electronic devices such as mobile phones and notebook computers, have recently become larger power storage devices (hereinafter referred to as secondary batteries and capacitors) for hybrid vehicles, electric vehicles, and power storage. Are collectively expected to be used for power storage devices), and improving the safety of lithium ion secondary batteries is an important issue.
  • a lithium ion secondary battery is a battery system in which lithium ions (Li + ) present in the active material of the positive electrode move to the negative electrode by charging, and return to the positive electrode again by discharging.
  • lithium ions Li +
  • Such a battery system was used before 1980 already proposed, specific ions are biased to the negative electrode (or positive electrode) in the charged state, and biased to the negative electrode (or positive electrode) in the discharged state, which is called “rocking chair battery”.
  • non-metallic minerals are generally called ceramics, but in these ceramic materials, electrochemical redox reactions can proceed reversibly with lithium ion doping and dedoping.
  • a ceramic material can be used as a positive electrode active material or a negative electrode active material of a lithium ion battery. Therefore, many lithium ion batteries may appear in the future depending on the combination.
  • Some of these ceramic materials are abundant in resources, and will be the key to reducing the price of future lithium ion batteries.
  • Active material in a power storage device means a material that directly contributes to a power storage reaction. Active materials in power storage devices are classified into those that reversibly chemically change based on electrochemical redox reactions and those that do not change chemically.
  • a power storage device that uses an active material that reversibly changes chemically based on an electrochemical redox reaction in an electrolyte solution for both a positive electrode active material and a negative electrode active material is a “secondary battery (or simply a battery). .) ".
  • an active material that changes chemically based on an electrochemical oxidation-reduction reaction is classified as a “capacitor” when the power storage device is used only for either the positive electrode or the negative electrode. Since an active material that is not based on chemical change is used for at least one of the positive electrode and the negative electrode for the capacitor, the storage capacity is smaller than that of the secondary battery, and it is not suitable for large power storage devices such as electric vehicles and power storage. is there.
  • the positive electrode and the negative electrode are electrodes in which each active material layer is formed in close contact with each current collector, and the active material in each active material layer is collected. Since it is necessary to be electrically connected to the electric body, the active material layer is made electronically conductive by mixing a conductive aid such as carbon. Therefore, it is necessary to prevent an internal short circuit between the positive electrode and the negative electrode by interposing a separator between the positive electrode and the negative electrode facing each other.
  • Internal short circuit between positive electrode and negative electrode is generally referred to as an internal short-circuit, but is a direct conduction between the positive electrode and the negative electrode facing each other.
  • Separatator in a power storage device means a separator function that is interposed between the positive electrode and the negative electrode facing each other, but “separator function” means that the electronic conduction between the positive electrode active material and the negative electrode active material is interrupted, Ion conduction is a function to ensure.
  • An “active material layer” in a power storage device is a porous body composed of an active material, and the active material that directly contributes to the power storage reaction smoothly transfers electrons to and from the external circuit and transmits ions to the counter electrode.
  • the molded body that can be used is usually formed in close contact with the current collector.
  • This “current collector” is an electron conductor that mediates transfer of electrons between the active material and an external circuit.
  • graphite or the like having an average particle size of about 5 to 10 ⁇ m is mixed in the active material layer as a conduction aid. Therefore, when the thickness of the separator layer is about 5 to 10 ⁇ m or less, such a conduction aid becomes conductive. It is sufficiently conceivable that the power storage device is short-circuited between the electrodes as a conductive foreign substance. Therefore, the thickness of the separator layer is desirably about 15 ⁇ m or more.
  • a sheet separator made of polyethylene (PE) or polypropylene (PP) having a thickness of about 25 ⁇ m or more is used as the separator.
  • a “sheet separator” is a sheet-like porous membrane interposed between a positive electrode and a negative electrode. However, if the sheet-like porous membrane is impregnated with an electrolyte solution, the ionic conduction between the positive electrode and the negative electrode is ensured and the separator It has a function.
  • Non-Patent Document 8 a method of forming a non-electron conductive (electronic insulating) ceramic layer on the electrode surface as a separator having high heat resistance has been proposed (see Non-Patent Document 8).
  • electronic insulating ceramic particles such as alumina (Al 2 O 3 ) are applied to the electrode surface as a slurry and dried, and the electronic insulating ceramic layer (porous ceramic layer) ) Can be formed on the electrode surface at low cost.
  • the electronic insulating ceramic layer formed on the electrode surface has pores, if the pores are filled with the electrolyte, ion conductivity is added and a “separator function” is provided. Therefore, it can be replaced with a conventional sheet-like separator, and is effective in improving the safety of the lithium ion battery and at the same time reducing the separator cost.
  • a material having an electric conductivity of less than 10 ⁇ 10 S / cm is said to be an insulator, and “electronic insulating” or “non-electron conductive” as used in this specification means an electronic conductivity of 10 It means less than ⁇ 10 S / cm, and an electron conductivity of 10 ⁇ 10 S / cm or more is usually classified as a semiconductor (electron conductivity is about 10 3 to 10 ⁇ 10 S / cm). Including in this specification, it is referred to as “electron conductivity”.
  • the ceramic layer formed on the electrode surface is formed with a thickness sufficient to prevent an internal short circuit between the positive electrode and the negative electrode (15 ⁇ m or more), the internal resistance of the power storage device increases. .
  • the ceramic layer is formed with a thickness (about 5 ⁇ m) at which the internal resistance of the power storage device falls within a satisfactory value, an internal short circuit between the positive electrode and the negative electrode cannot be sufficiently prevented with the ceramic layer alone.
  • the present invention has been made in view of the above problems, and an object of the present invention is to provide a power storage device in which an internal short circuit is sufficiently prevented and an internal resistance is sufficiently low using a ceramic layer having high heat resistance as a separator.
  • the power storage device of the present invention is a power storage device in which a positive electrode and a negative electrode face each other, and the positive electrode and the negative electrode both have an electron conductive active material layer formed on a current collector.
  • the internal short circuit between the opposing positive electrode and the negative electrode is prevented by an electronic insulating ceramic layer interposed between the active material layers of the opposing positive electrode and the negative electrode, and the ceramics constituting the ceramic layer.
  • the particles are selected from electronically insulating ceramics that can be chemically changed by an electrochemical reduction reaction.
  • an internal short circuit between the opposing positive electrode and the negative electrode is prevented by an electronic insulating ceramic layer interposed between the active material layer of the opposing positive electrode and the negative electrode, and ions between the positive electrode and the negative electrode Conductivity is basically secured by the electrolyte solution impregnated in the ceramic layer.
  • the ceramic particles constituting the ceramic layer have an electronic insulating property that can be chemically changed by an electrochemical reduction reaction. Since it is selected from ceramics, the ceramic particles constituting the ceramic layer undergo an electrochemical reduction reaction from the particles in contact with the negative electrode, and all particles other than the ceramic particles in direct contact with the positive electrode are electrochemically reduced. As a result, it is changed to ion conductive ceramic particles.
  • the ionic conduction between the positive electrode and the negative electrode is greatly improved because it is carried by the electrolyte solution impregnated in the ceramic layer and the ceramic particles changed to ionic conductivity, and the thickness of the ceramic layer is increased only by the ceramic layer. It becomes possible to make it the thickness which can fully prevent the internal short circuit of the negative electrode.
  • the ceramic particles that are in direct contact with the positive electrode are not reduced because the potential of the positive electrode is applied, always remain electronically insulating, and play a role of preventing an internal short circuit between the positive electrode and the negative electrode.
  • Typical examples of the electronic insulating ceramic that can be chemically changed by an electrochemical reduction reaction include titanium oxides represented by the chemical formulas Li 4 Ti 5 O 12 and TiO 2 —B, which can be applied to the present invention.
  • titanium oxides represented by the chemical formulas Li 4 Ti 5 O 12 and TiO 2 —B which can be applied to the present invention.
  • One of the typical ceramic materials One of the typical ceramic materials.
  • Li 4 Ti 5 O 12 is electronically insulating because all Ti in the crystal is tetravalent (Ti 4+ ) and electrons cannot be transferred between Ti 4+ , but Li 4 + 3 Ti 3+ 3 In the crystal of Ti 4+ 2 O 12 , Ti 4+ and Ti 3+ are mixed and electrons can be exchanged and become electron conductive.
  • the power storage device is characterized in that the ceramic layer is formed on the surface of the active material layer of the negative electrode.
  • the electronic insulating ceramic layer interposed between the opposing positive electrode and negative electrode active material layers only needs to be interposed between the positive electrode and negative electrode active material layers in order to prevent internal short circuit between the positive electrode and negative electrode.
  • the power storage device with an electrode structure according to the present invention uses an ceramic layer having high heat resistance as a separator, sufficiently prevents internal short circuit, and has sufficiently low internal resistance.
  • FIG. 1 is a perspective view of a power storage element 10 (hereinafter also referred to as “electrode laminate 10”) according to an embodiment of the present invention.
  • FIG. 2 is a perspective view of a power storage device 100 according to an embodiment of the present invention.
  • the power storage element 10 shown in FIG. 1 contains an organic electrolyte (not shown) and is sealed in a laminate sheet 11 and a laminate sheet 12. It is a perspective view of the electrical storage apparatus 100 formed.
  • FIG. 3 is a cross-sectional view of a power storage device according to an embodiment of the present invention, in which a cross section DD ′ of the power storage device 10 shown in FIG. It is sectional drawing.
  • FIG. 4 is a cross-sectional view of the power storage device 10 after the initial charging of the power storage device according to the embodiment of the present invention.
  • the cross section DD ′ of the power storage device 10 shown in FIG. FIG. 5 is an enlarged cross-sectional view of an electrode end portion, with parts omitted.
  • the ceramic layer 5 made of electronic insulating ceramic particles is interposed between the positive electrode 31 and the negative electrode 32 facing each other, and the electronic insulation that constitutes the ceramic layer.
  • the ceramic particles are selected from electronically insulating ceramics that can be chemically changed by an electrochemical reduction reaction in an organic electrolyte.
  • the power storage element 10 is configured by alternately stacking positive electrodes 31 and negative electrodes 32, and the positive electrode 31 is an electronically conductive active material layer 2 composed of a positive electrode active material and a conductive assistant.
  • positive electrode active material layer 2 is an electrode formed in close contact with the current collector 4 (hereinafter also referred to as “positive electrode current collector 4”), and constitutes the active material layer 2
  • the positive electrode active material is electronically connected to the current collector 4.
  • the negative electrode 32 also has an electron conductive active material layer 1 (hereinafter also referred to as “negative electrode active material layer 1”) composed of a negative electrode active material and a conduction aid, and a current collector 3 (hereinafter referred to as “negative electrode collector”).
  • the negative electrode active material constituting the active material layer 1 is electronically connected to the current collector 3. However, the electronic continuity between the positive electrode active material in the positive electrode active material layer 2 and the negative electrode active material in the negative electrode active material layer 1 is the electronic insulating ceramic layer 5 formed on the surface of the negative electrode active material layer 1. It has been refused.
  • the positive electrode active material layer 2 the negative electrode active material layer 1, and the ceramic layer 5 have pores, and the pores are filled with the electrolytic solution, the positive electrode active material layer 2 and the negative electrode active material layer 1.
  • the insulating ceramic layer 5 has a separator function because the positive electrode active material layer 2 and the negative electrode active material layer 1 are turned off by ionic conduction without being electrically connected. Therefore, when a voltage that makes the current collector 4 positive is applied to the current collector 4 and the current collector 3, the positive electrode active material constituting the positive electrode active material layer 2 is electrochemically oxidized, and the negative electrode active material layer 1 The negative electrode active material constituting is reduced electrochemically.
  • the negative electrode 32 is stacked so that the vertical and horizontal dimensions are larger by 2 A than the positive electrode 31, and the electrode end of the negative electrode 32 is positioned outside the electrode end of the positive electrode 31 by the dimension A.
  • the electrode end of the negative electrode 32 can be prevented from short-circuiting with the positive electrode 31.
  • the insulating member 8 it is possible to prevent a short circuit between the electrode end of the negative electrode 32 and the exposed portion 34 of the positive electrode current collector.
  • any exposed portion 33 of the current collector provided on each electrode of the negative electrode 32 is welded to the negative electrode tab 6, and any exposed portion 34 of the current collector provided on each electrode of the positive electrode 31 is welded to the positive electrode tab 7. . Since the plastic tape 9 is preliminarily bonded to the electrode tab 6 and the electrode tab 7 by thermocompression bonding, when the electricity storage element 10 is sealed with the laminate sheet 11 and the laminate sheet 12 as shown in FIG. 9 is integrated with the laminate sheet 11 and the laminate sheet 12 and heat-sealed, so that the negative electrode tab 6 and the positive electrode tab 7 are taken out to the outside without disturbing the sealing of the electricity storage element 10 and the negative electrode external terminal 13 and the positive electrode external It becomes terminal 14.
  • the electrode laminate (power storage element) 10 includes the “negative electrode active material layer 1” and the “electronic insulating ceramic layer 5” as shown in FIG. 3. ”,“ Positive electrode active material layer 2 ”are arranged in this order, and the vacancies of all the layers are filled with the electrolyte solution.
  • the positive electrode active material in 2 conducts by ionic conduction.
  • the electrode laminate 10 is formed of the ceramic particles constituting the ceramic layer 5 among the particles directly contacting the negative electrode active material layer 1 as shown in FIG. Therefore, the ceramic particles are electrochemically reduced to be transformed into ceramic particles having ion conductivity and electron conductivity. Furthermore, since the potential of the negative electrode is applied to the ceramic particles that are not in direct contact with the negative electrode active material layer 1 through the particles that have changed to electron conductivity, an electrochemical reduction reaction occurs in a chained manner. Most of 5 is changed to a conductive ceramic layer 51 composed of ceramic particles having ion conductivity and electron conductivity. In the following description, when it is based on ion conductivity or ion conductivity and electron conductivity, it is expressed as “conductivity”, and when it is based only on electron conductivity, it is expressed as “conductivity”.
  • the electrochemical reduction reaction of the crystal in the organic electrolyte is that electrons and cations (Li ions) are continuously injected into the crystal (Coulomb / s). If electrons and cations (Li ions) cannot move freely in the crystal body by an electrochemical reduction reaction, the electrochemical reduction reaction does not proceed into the crystal. Therefore, the electron-insulating crystal that can be electrochemically reduced is a crystal that can continuously inject electrons and cations (Li ions) into the crystal (Coulomb / s). If such a crystal is electrochemically reduced, electrons and cations (Li ions) can move freely in the crystal as a result of injection of electrons and cations (Li ions). That is, an electronically insulating crystalline substance that can be reduced electrochemically can be converted into a crystalline substance having electronic conductivity and ionic conductivity if electrochemically reduced.
  • the ceramic particles constituting the ceramic layer 5 are selected from electronically insulating ceramics that can be electrochemically reduced, the ceramic particles change into ceramics having ionic conductivity by electrochemical reduction.
  • the ceramic particles constituting the ceramic layer 5 are in direct contact with the positive electrode active material layer 2 among the ceramic particles constituting the ceramic layer 5 although they are electronically insulating ceramics that can be reduced electrochemically. Since the positive electrode potential is applied to the particles, the ceramic particles are not electrochemically reduced. Therefore, the particles in direct contact with the positive electrode active material layer 2 always remain electronically insulating and remain as “non-electron conductive (electronic insulating) ceramic layer 50” as shown in FIG.
  • Non-electron conductive ceramics that can be electrochemically reduced in an organic electrolyte include Li 4 Ti 5 O 12 and TiO 2 —B.
  • Li 4 Ti 5 O 12 and TiO 2 —B are materials that have been actively studied as negative electrode active materials for lithium ion batteries and capacitors (see Non-Patent Documents 2 to 7), but have a separator function. There is no example of study as a ceramic material.
  • FIG. 5 is a schematic view showing a cross section of the ceramic layer 5 before charging (left in the figure) and after charging (right in the figure) in the power storage device according to the embodiment of the present invention. Specifically, the case where Li 4 Ti 5 O 12 is used as the non-electron conductive ceramic particles is shown.
  • the electronically conductive negative electrode active material layer 1 and the electronically conductive positive electrode active material layer 2 are electronically insulating ceramic layers composed of electronically insulating Li 4 Ti 5 O 12. 5, the electronic continuity is completely cut off, and in the first charge, the negative electrode active material constituting the negative electrode active material layer 1 is electrochemically reduced, and the positive electrode active material constituting the positive electrode active material layer 2 is It is electrochemically oxidized and charged.
  • the Li 4 Ti 5 O 12 particles that are in direct contact with the positive electrode active material layer 2 are not subjected to electrochemical reduction because of the positive electrode potential, and Li 4 Ti 5 O as it is.
  • the “non-electron conductive ceramic layer 50” is configured as 12 particles, the Li 4 Ti 5 O 12 particles capable of direct or indirect electronic conduction with the negative electrode active material layer 1 have a negative electrode potential. Then, it is electrochemically reduced to Li 4 + X Ti 4+ 5-X Ti 3+ X O 12 (0 ⁇ X ⁇ 3), and the ceramic layer 51 is formed after the first charge (right side in the figure).
  • the ceramic layer 51 has good ion conductivity due to excess Li ions (Li + 4 + X ) in the crystal, and also has good electron conductivity based on the exchange of free electrons of Ti 4+ and Ti 3+ . Good ionic conductivity enhances the separator function, but good electronic conductivity can also break the separator function. However, since the electronic conduction between the negative electrode active material layer 1 and the positive electrode active material layer 2 is completely interrupted by the ceramic layer 50, there is no concern that the electronic conductivity of the ceramic layer 51 breaks the separator function of the ceramic layer 5.
  • the ceramic layer 5 interposed between the negative electrode active material layer 1 and the positive electrode active material layer 2 is mostly transformed into the ceramic layer 51 as shown in FIG.
  • the internal resistance of the power storage device is lowered by the amount of the separator function, particularly the ion conductivity.
  • the electrical storage element 10 which concerns on one Embodiment of this invention shown in FIG. 3 showed the case where the nonelectroconductive ceramic layer 5 was formed on the negative electrode active material layer 1, the ceramic layer 5 is comprised.
  • the ceramic particles are electrochemically reduced to change to ionic conductivity, and the ceramic layer 5 is formed on the negative electrode active material layer 1 so that the ceramic particles are electrochemical. This is advantageous in that it is susceptible to reduction.
  • the ceramic layer 5 is formed on the positive electrode active material layer 2
  • the ceramic layer 5 inevitably comes into contact with the negative electrode active material layer 1 if the negative electrode active material layer 1 and the positive electrode active material layer 2 face each other. Therefore, there is a possibility that the ceramic particles in contact with the negative electrode active material layer 1 are electrochemically reduced. Therefore, the formation of the ceramic layer 5 on the positive electrode active material layer 2 is not denied.
  • the conventional sheet-like separator Since the conventional sheet-like separator has a very porous structure, it has a high ability to hold an electrolytic solution and ensures good ion conduction.
  • the ionic conduction between the negative electrode 32 and the positive electrode 31 is basically determined by the electrolyte contained in the ceramic layer.
  • the porosity of such a ceramic layer is generally less than half that of the current sheet-like separator, the internal resistance of the power storage device is increased unless the ceramic layer 5 is made considerably thin. turn into.
  • the ceramic layer 5 is made of insulating ceramic particles that are not oxidized or reduced electrochemically in an organic electrolyte such as alumina (Al 2 O 3 ), so that it is placed in a charged state. Even if this is done, the ionic conductivity of the ceramic layer 5 does not increase, and the internal resistance of the power storage device increases at the same thickness (about 25 ⁇ m) as the sheet separator.
  • the ionic conductivity between the negative electrode 32 and the positive electrode 31 is only the ionic conductivity of the electrolyte contained in the ceramic layer 5 (the ceramic layers 51 and 50 after the first charge is completed). It is ensured not only by the ionic conductivity of the ceramic particles constituting the ceramic layer 51. Therefore, even when the ceramic layer 5 is formed with a thickness that can sufficiently prevent a short circuit between the positive electrode and the negative electrode, the internal resistance of the power storage device can be kept low.
  • the electronic short circuit between the negative electrode 32 and the positive electrode 31 is prevented by ceramic particles composed of ceramic particles that remain electronically insulating.
  • the ceramic layer 51 which is the layer 50 and is electronically conductive, does not have the ability to prevent an electronic short circuit between the negative electrode 32 and the positive electrode 31.
  • the thickness of the ceramic layer 5 initially formed on the electrode is greatly related to the ability to prevent the electronic short circuit between the negative electrode 32 and the positive electrode 31.
  • the thickness of the separator layer interposed between the positive electrode and the negative electrode is thin, there is a high possibility that the power storage device will cause an internal short even if a very small conductive foreign matter is sandwiched between the positive electrode and the negative electrode. If the thickness of the separator layer is about 5 to 10 ⁇ m, graphite or the like (average particle size of about 5 to 10 ⁇ m) mixed with the active material layer as a conduction aid is usually used as a conductive foreign substance between the electrodes. It is fully conceivable that the power storage device may be short-circuited due to being caught.
  • the thickness of the ceramic layer 5 is thin (about 5 to 10 ⁇ m), the risk of the power storage device being short-circuited is naturally high.
  • FIG. 6 is a schematic diagram of electrodes showing the difference in occurrence of internal short circuit due to the difference in thickness of the ceramic layer 5 in the embodiment of the present invention.
  • FIG. 6A shows the case where the thickness (t1) of the ceramic layer 5 is thin (about 5 to 10 ⁇ m or less).
  • 6 (b) and 6 (c) show the case where the thickness (t2) of the ceramic layer 5 is thick (15 ⁇ m or more),
  • FIG. 6 (b) shows the state before the first charge, and FIG. After the first charge.
  • the ceramic layer 5 interposed between the negative electrode active material layer 1 and the positive electrode active material layer 2 is thin (t1), the internal resistance of the power storage device is reduced. Then, the negative electrode active material layer 1 and the positive electrode active material layer 2 are short-circuited with the conductive foreign matter 60 sandwiched therebetween, and the risk that the power storage device is short-circuited is increased.
  • the positive electrode potential is applied to the ceramic particles that are in direct contact with the positive electrode active material layer 2 and the conductive foreign material 60. Therefore, the ceramic particles remain electronically insulative without being reduced electrochemically, and the electronically insulating ceramic particles constitute the electronically insulating ceramic layer 50.
  • the ceramic particles that are not in direct contact with the positive electrode active material layer 2 and the conductive foreign material 60 are electrochemically reduced to form the ion conductive ceramic layer 51, the negative electrode active material layer 1 and the positive electrode active material layer 2
  • the ionic conduction between them is not only the ionic conductivity of the electrolyte contained in the ceramic layer 5 (after the first charge, the ceramic layers 51 and 50), but also the ionic conduction of the ceramic particles constituting the ceramic layer 51. Also secured by gender. Therefore, even when the ceramic layer 5 is formed with a thickness that can sufficiently prevent a short circuit between the positive electrode and the negative electrode (FIGS. 6B and 6C), the internal resistance of the power storage device can be kept low.
  • a power storage device there are electronic insulating ceramic particles such as Li 4 Ti 5 O 12 and TiO 2 that can be electrochemically reduced in an organic electrolyte, and a negative electrode of a lithium ion battery.
  • electronic insulating ceramic particles such as Li 4 Ti 5 O 12 and TiO 2 that can be electrochemically reduced in an organic electrolyte, and a negative electrode of a lithium ion battery.
  • a lithium ion battery with sufficiently low internal resistance and high safety can be realized.
  • the industrial value of the electrode structure according to the present embodiment is particularly high because a lithium ion battery with sufficiently low internal resistance, high safety, and low price can be provided for a large-scale power storage device such as a hybrid vehicle, an electric vehicle, or a power storage device. It ’s big.
  • a rocking chair battery using spinel lithium manganese oxide (LiMn 2 O 4 ) as a positive electrode active material and spinel lithium titanium oxide (Li 4 Ti 5 O 12 ) as a negative electrode active material In general, the electrode structure shown in FIG. 3 is applied.
  • the electrode stack (electric storage element) 10 is configured by alternately stacking positive electrodes 31 and negative electrodes 32 without interposing a sheet-like separator.
  • the positive electrode 31 is an electrode in which an electron conductive active material layer 2 composed of an active material and a conduction aid is formed in close contact with the positive electrode current collector 4, and the negative electrode 32 is also composed of an active material and a conduction aid.
  • the electronic insulating ceramic layer 5 is formed on the surface of the electron conductive negative electrode active material layer 1, so that the positive electrode 31 and the negative electrode 32 facing each other in the electrode stack 10 are not electrically connected. .
  • the electronic insulating ceramic layer 5 formed on the electrode surface of the negative electrode 32 is composed of Li 4 Ti 5 O 12 which is the same as the negative electrode active material.
  • Li 4 Ti 5 O 12 is a completely electronic insulating material having a small electronic conductivity (about 10 ⁇ 13 s / cm), and is reduced in an organic electrolytic solution to have both good electronic conductivity and ionic conductivity. Since it changes to 7 Ti 5 O 12 , it is a ceramic material that is particularly well suited to one embodiment of the present invention.
  • Li 4 Ti 5 O 12 is a container of alumina in which lithium hydroxide (LiOH) and titanium dioxide (TiO 2 ) are mixed well in a molar ratio of 4: 5, pressed into a pellet, and nickel foil is spread. And synthesized by firing at 800 ° C. in a helium atmosphere. There is no unreacted TiO 2 in the XRD pattern of the composite, and it is a Li 4 Ti 5 O 12 single layer. In the SEM photograph (magnification 6600) of the composite, primary particles of about 0.2 to 1 ⁇ m are gathered and 1 It was confirmed that secondary particles of about 15 ⁇ m were formed. The particle size of Li 4 Ti 5 O 12 was adjusted such that 90% was 6.78 ⁇ m or less and 1.14 ⁇ m or less was 10%.
  • 89 parts by weight of the prepared Li 4 Ti 5 O 12 was mixed with 2 parts by weight of acetylene black and 3 parts by weight of graphite as a conductive aid, and 6 parts by weight of PVDF (polyvinylidene fluoride) as a binder was dissolved.
  • a slurry is prepared by wet mixing with a solvent. This slurry was uniformly applied with a coating width of 170 mm and dried on one side of an aluminum foil having a width of 200 mm and a thickness of 0.02 mm, leaving uncoated portions of 15 mm on both ends, and then the same on the other side. After coating with a coating width and drying, a belt-shaped negative electrode in which the negative electrode active material layer 1 is in close contact with the current collector 3 by pressing with a roller press so that the thickness is 0.15 to 0.16 mm. Is made.
  • an electronic insulating ceramic layer 5 is further formed on the electrode surface.
  • Li 4 Ti 5 O 12 prepared as described above was also used for the ceramic particles constituting the insulating ceramic layer 5.
  • the adjusted Li 4 Ti 5 O 12 is made into an aqueous slurry using a CMC aqueous binder, and this slurry is formed on both sides of the belt-like negative electrode so that the thickness of the ceramic layer on one side is about 25 ⁇ m.
  • the active material layer 1 was applied so as to completely cover and dried to form an electronic insulating ceramic layer 5 on the electrode surface of the strip-shaped negative electrode.
  • the strip-shaped negative electrode on which the insulating ceramic layer 5 is formed leaves the uncoated portion of the current collector as 10 ⁇ 20 mm as the electrode tab mounting portion 33, and is cut into a size of 170 ⁇ 110 mm in the ceramic layer coating area.
  • a final negative electrode 32a was prepared.
  • LiMn 2 O 4 used as the positive electrode active material was prepared by firing a mixture of manganese dioxide and lithium carbonate in air at 850 ° C. and then using a conventional synthesis method. However, the LiMn 2 O 4 synthesized here agrees well with the diffraction pattern of spinel type LiMn 2 O 4 in X-ray diffraction. It is thought that Li 1.05 Mn 1.95 O 4 substituted with lithium. The particle size of LiMn 2 O 4 was adjusted so that 90% was 12.94 ⁇ m or less and 3.52 ⁇ m or less was 10%.
  • the uncoated portion of the current collector is left as an electrode tab attachment portion 15 ⁇ 20 mm, and is cut into a size of 160 ⁇ 100 mm in the coated area of the positive electrode active material layer 2 to obtain a final positive electrode 31a. Prepared.
  • the positive electrode 31 a and the negative electrode 32 a prepared as described above are composed of three negative electrodes 32 and two positive electrodes 31 with the electrode end of the negative electrode 32 a having a dimension A (here, 5 mm).
  • the exposed portion 34 of the positive electrode current collector provided on the positive electrode 31 and the exposed portion 33 of the negative electrode current collector provided on the negative electrode 32 are respectively connected to the positive electrode 31 as shown in FIG.
  • the tab 7 and the negative electrode tab 6 are welded together, the power storage element 10 shown in FIG. 1 is obtained.
  • the power storage element 10 is sandwiched between the laminate sheet 11 and the laminate sheet 12, and the periphery 112 a of the laminate sheet is heat-sealed. At this time, since a portion 112b around the laminate sheet is not heat-sealed, the power storage element 10 is in a state where the laminate sheet 11 and the laminate sheet 12 are contained in the bag.
  • a mixed solution of ethylene carbonate (EC) and diethyl carbonate (DEC) in which 1 mol / L LiPF 6 is dissolved is injected as an electrolyte with the unsealed portion 112b of the bag facing up, and vacuum impregnation method
  • the storage element 10 in the bag is impregnated with an electrolytic solution. Thereafter, the unsealed portion 112b of the laminate sheet was sealed under vacuum, and a lithium ion battery A having a structure shown in FIG. 2 was produced with an outer dimension of 210 mm ⁇ 140 mm ⁇ 1.4 mm.
  • the electrical storage element 10 is preliminarily bonded with a plastic tape 9 on the electrode tab 6 and the electrode tab 7, the plastic tape 9 is integrated with the laminate sheet 11 and the laminate sheet 12. Since the heat bonding is performed, the negative electrode tab 6 and the positive electrode tab 7 do not hinder the sealing of the electric storage element 10, and the negative electrode tab 6 and the positive electrode tab 7 are taken out to the outside, and the negative electrode external terminal 13 and the positive electrode external terminal 14, respectively. It becomes.
  • the completed lithium ion battery A was aged for 24 hours, then charged at 0.1 A for the first charge, set the upper limit of the charge voltage to 3.0 V, and charged for 20 hours. As a result of discharging with current, a discharge capacity of about 1.5 Ah was obtained.
  • the internal resistance of the completed lithium ion battery A was about 180 m ⁇ at the AC impedance measured at a frequency of 1 kHz before the first charge, but the AC impedance measured at a frequency of 1 kHz after the first charge. Decreased to about 36 m ⁇ , and the internal resistance of about 36 m ⁇ was maintained during the subsequent charge / discharge regardless of the state of charge / discharge (SOC: State of Charge).
  • the ceramic layer 5 formed on the electrode surface of the negative electrode 32 is composed of the insulating ceramic layer 50 and the conductive ceramic when the first charging is completed.
  • the insulating ceramic layer 50 is separated into the layer 51 and functions as a substantial separator.
  • Li 4 Ti 5 O 12 which is the negative electrode active material in the negative electrode active material layer 1 is electrochemically reduced (charged) to Li 7 Ti 5 O 12 at the end of charging, but the conductive ceramics. Also in the layer 51, Li 4 Ti 5 O 12 is electrochemically reduced to become conductive (electron conductive and ion conductive) Li 7 Ti 5 O 12 , and the ceramic layer 51 It can function substantially as a negative electrode active material layer.
  • the active material constituting the negative electrode active material layer 1 is the same material as the ceramic particles constituting the ceramic layer 5 as in this embodiment, or the redox potential of the same level as the ceramic particles constituting the ceramic layer 5.
  • the charge / discharge capacity of the power storage device is increased by adding the charge / discharge capacity of the conductive ceramic layer 51 to the charge / discharge capacity of the negative electrode active material layer 1. is there.
  • a ceramic layer formed on the electrode surface of the negative electrode is composed of alumina (Al 2 O 3 ) particles, which are general ceramics, to produce a lithium ion battery B, which is compared with the battery of Example 1.
  • the positive electrode 31a prepared in Example 1 is used as it is as the positive electrode.
  • the negative electrode uses the strip-shaped negative electrode prepared in Example 1, and alumina (Al 2 O 3 ) particles are used as CMC.
  • An aqueous ceramic binder is used to form an aqueous slurry, and using this slurry, the insulating ceramic layer 5b is formed with the same thickness (about 25 ⁇ m) as in Example 1 and has the same dimensions as in Example 1.
  • the negative electrode 32b was cut.
  • Example 2 Two of the prepared negative electrodes 32b and two of the positive electrodes 31a prepared in Example 1 are stacked, and the electricity storage device 10 is assembled in the same manner as in Example 1, and all the others are the same as in Example 1, and FIG. A lithium ion battery B having the structure shown in FIG. 2 was produced with an outer dimension of 210 mm ⁇ 140 mm ⁇ 1.4 mm.
  • the completed lithium-ion battery B is also subjected to aging for 24 hours, charging with 0.1 A current, charging voltage at the upper limit of 3.0 V, charging for 20 hours, and discharging with constant current of 0.2 A.
  • a discharge capacity of about 1.3 Ah was obtained, but the internal resistance of this battery was about 180 m ⁇ in AC impedance measured at a frequency of 1 kHz even after the first charge, and in the subsequent charge / discharge Regardless of the charge / discharge state (SOC: State of Charge), the internal resistance did not become 180 m ⁇ or less.
  • the internal resistance is 5 times that of Example 1, and the internal resistance is higher than that of a battery using a conventional resin separator.
  • the value of is 2.5 times.
  • the insulating ceramic layer 5 formed on the electrode surface of the negative electrode 32 is composed of Li 4 Ti 5 O 12 as its constituent ceramic particles as in Example 1.
  • PVDF polyvinylidene fluoride
  • a slurry is prepared by wet mixing with a solvent in which parts by weight are dissolved. Apply this slurry uniformly on one side of a 200 mm wide and 0.01 mm thick copper foil with a coating width of 170 mm, leaving 15 mm uncoated parts at both ends, and then apply the same to the other side.
  • a belt-like carbon negative electrode was produced by pressing with a roller press to a thickness of 0.13 to 0.15 mm.
  • the formation of the insulating ceramic layer on the surface of the belt-like carbon negative electrode uses a slurry using a Li 4 Ti 5 O 12 aqueous binder as in Example 1. This slurry is applied to both sides of the band-shaped carbon negative electrode so that the thickness of the ceramic layer on one side is about 25 ⁇ m and the carbon coating layer is completely covered and dried, and is insulated on the surface of the band-shaped carbon negative electrode The characteristic ceramic layer 5 was formed.
  • the strip-shaped carbon negative electrode having the insulating ceramic layer 5 formed on the electrode surface leaves the uncoated portion of the current collector as the electrode tab mounting portion 33, and the size of the ceramic layer is 170 ⁇ 110 mm.
  • the negative electrode 32c was prepared by cutting.
  • the prepared negative electrode 32c and the positive electrode 31a prepared in Example 1 were manufactured in the same manner as in Example 1 with a battery structure shown in FIG. 2 and a lithium ion battery C having an outer dimension of 210 mm ⁇ 140 mm ⁇ 1.4 mm.
  • the internal resistance of the completed lithium ion battery C was about 180 m ⁇ in AC impedance measured at a frequency of 1 kHz before the first charge.
  • the initial charge is 0.1A, and the upper limit of the charge voltage is set to 4.2V.
  • the battery is charged for 20 hours and discharged at a constant current of 0.2A. Capacity was obtained.
  • the AC impedance measured at a frequency of 1 kHz decreases to about 36 m ⁇ , and the charge and discharge after that is almost independent of the state of charge (SOC) and has an internal resistance of about 36 m ⁇ . Is still about half of the internal resistance of a conventional lithium ion battery.
  • Examples 1 and 2 one embodiment of the lithium ion battery using LiMn 2 O 4 as the positive electrode active material and Li 4 Ti 5 O 12 and carbon as the negative electrode active material was shown.
  • the positive electrode active material and the negative electrode active material are not limited to this, and the above embodiment shows one of application examples of the present invention, and the technical scope of the present invention is a specific configuration of the above embodiment. It is not intended to be limited to. Various modifications can be made without departing from the scope of the present invention.
  • resin separators used in lithium ion batteries have poor heat resistance, which is a factor that reduces the safety of batteries.
  • the material cost of the battery is greatly increased.
  • such a resin separator is unnecessary, and a highly heat-resistant ceramic layer having a good separator function can be formed on the electrode surface at a low cost, thereby providing an inexpensive and highly safe lithium ion battery. it can.
  • the power storage device of the present invention uses an ceramic layer having high heat resistance as a separator, sufficiently prevents internal short circuit, and has sufficiently low internal resistance.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Cell Separators (AREA)

Abstract

La présente invention concerne un dispositif de stockage d'énergie électrique dans lequel des particules de céramique constituant une couche céramique électroniquement isolante sont choisies parmi des céramiques électroniquement isolantes pouvant être soumises à une réduction électrochimique dans une solution électrolytique organique. Des particules de céramique en contact avec une électrode positive restent donc électroniquement isolantes tandis que les particules de céramique restantes subissent une réduction électrochimique et acquièrent une conductivité ionique, maintenant une faible résistance interne dans ce dispositif de stockage d'énergie électrique malgré l'utilisation d'une couche céramique en tant que séparateur.
PCT/JP2014/061163 2013-04-24 2014-04-21 Dispositif de stockage d'énergie électrique WO2014175212A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109546063A (zh) * 2018-12-13 2019-03-29 许昌学院 一种锂离子电池复合隔离膜

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Publication number Priority date Publication date Assignee Title
JP6877202B2 (ja) * 2016-12-28 2021-05-26 太陽インキ製造株式会社 ネガ型光硬化性樹脂組成物、ドライフィルム、硬化物およびプリント配線板
KR20210075530A (ko) 2019-12-13 2021-06-23 현대자동차주식회사 헤어핀 타입 고정자 코일 성형 시스템용 코일 밴딩 장치

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008021635A (ja) * 2006-06-14 2008-01-31 Nissan Motor Co Ltd 非水電解質二次電池用電極およびこれを用いた非水電解質二次電池
JP2009099558A (ja) * 2007-09-25 2009-05-07 Panasonic Corp 二次電池
JP2010086711A (ja) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd 非水電解液二次電池用電極板、非水電解液二次電池用電極板の製造方法、および非水電解液二次電池
WO2014087895A1 (fr) * 2012-12-03 2014-06-12 永浦 敦子 Dispositif d'accumulation, véhicule hybride, et véhicule électrique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008021635A (ja) * 2006-06-14 2008-01-31 Nissan Motor Co Ltd 非水電解質二次電池用電極およびこれを用いた非水電解質二次電池
JP2009099558A (ja) * 2007-09-25 2009-05-07 Panasonic Corp 二次電池
JP2010086711A (ja) * 2008-09-30 2010-04-15 Dainippon Printing Co Ltd 非水電解液二次電池用電極板、非水電解液二次電池用電極板の製造方法、および非水電解液二次電池
WO2014087895A1 (fr) * 2012-12-03 2014-06-12 永浦 敦子 Dispositif d'accumulation, véhicule hybride, et véhicule électrique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109546063A (zh) * 2018-12-13 2019-03-29 许昌学院 一种锂离子电池复合隔离膜
CN109546063B (zh) * 2018-12-13 2021-06-22 许昌学院 一种锂离子电池复合隔离膜

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